Síntese e caracterização de complexo tetranuclear de cobre com o ligante resorcinareno

The main objective of the present work is to contribute to the development of the coordination chemistry of macromolecules such as resorcinarene with the synthesis and characterization of new copper complexes with chloride, vanillin and resorcinarene binders, all coordinated to phenanthroline, a biologically active molecule with important properties in biological systems. The complex [(Cu(phen))4(resvan)], was synthesized from the direct reaction of the metals with resorcinarene and generates several possibilities for coordination, which hinders its characterization. Therefore, in order to limit the coordination sites of the ligand, the complex [(Cu(phen))4(resvan)]Cl4 was formed from a new synthetic methodology. The complex cis-[Cu(phen)Cl2], cis-[Cu(phen)(van)]Cl, [(Cu(phen))4(resvan)] and [(Cu(phen))4(resvan)]Cl4 were characterized by spectroscopic techniques such as IR, UV-vis and EPR. By using infrared it has been possible to demonstrate the presence of the phenanthroline ligand in the synthesized complexes, and vanillin in the complex cis- [Cu(phen)(van)]Cl and resvan ligand in the complex [(Cu(phen))4(resvan)], besides this indicating the formation of resorcinarene in the complex [(Cu(phen))4(resvan)]Cl4. The electronic spectra of these coordination compounds indicated the presence of the phenanthroline ligand, by its intense bands in the ultraviolet region. For the complex cis- [Cu(phen)(van)]Cl it still indicated the presence of the ligand vanillin based on intraligand bands of vanillin and charge transfer, LMCT. Furthermore, the spectra showed d-d bands, confirming the formation of metal compounds. The amount of copper atoms present in the complex [(Cu(phen))4(resvan)]Cl4 was estimated from a comparative analysis of the absorbances of solutions of the same concentration of [(Cu(phen))4(resvan)]Cl4 and cis- [Cu(phen)(van)]Cl, which indicates that these compounds have copper atoms in the ratio 4:1. The EPR spectra of the complex cis-[Cu(phen)Cl2], cis-[Cu(phen)(van)]Cl and [(Cu(phen))4(resvan)]Cl4 showed axial profiles, while the complex [(Cu(phen))4(resvan)] showed of axial and rhombic profiles, indicating a change in the symmetry of the Cu (II) to this complex environment. The binders vanillin and resvan underwent biological assays with satisfactory results, both exhibited antioxidant activity and low toxicity, as well vanillin present antitoxoplásmico character.

Desenvolvimento de metodologia de extração e pré-concentração utilizando sistema microemulsionado para determinação de Cd, Co, Cu, Ni, Pb e Tl em águas naturais e produzidas por HR-CS AAS

The determination and monitoring of metallic contaminants in water is a task that must be continuous, leading to the importance of the development, modification and optimization of analytical methodologies capab le of determining the various metal contaminants in natural environments, because, in many cases, the ava ilable instrumentation does not provide enough sensibility for the determination of trace values . In this study, a method of extraction and pre- concentration using a microemulsion system with in the Winsor II equilibrium was tested and optimized for the determination of Co, Cd, P b, Tl, Cu and Ni through the technique of high- resolution atomic absorption spectrometry using a continuum source (HR-CS AAS). The optimization of the temperature program for the graphite furnace (HR-CS AAS GF) was performed through the pyrolysis and atomization curves for the analytes Cd, Pb, Co and Tl with and without the use of different chemical modifiers. Cu and Ni we re analyzed by flame atomization (HR-CS F AAS) after pre-concentr ation, having the sample introduction system optimized for the realization of discrete sampling. Salinity and pH levels were also analyzed as influencing factors in the efficiency of the extraction. As final numbers, 6 g L -1 of Na (as NaCl) and 1% of HNO 3 (v/v) were defined. For the determination of the optimum extraction point, a centroid-simplex statistical plan was a pplied, having chosen as the optimum points of extraction for all of the analytes, the follo wing proportions: 70% aqueous phase, 10% oil phase and 20% co-surfactant/surfactant (C/S = 4). After extraction, the metals were determined and the merit figures obtained for the proposed method were: LOD 0,09, 0,01, 0,06, 0,05, 0,6 and 1,5 μg L -1 for Pb, Cd, Tl, Co, Cu and Ni, re spectively. Line ar ranges of ,1- 2,0 μg L -1 for Pb, 0,01-2,0 μg L -1 for Cd, 1,0 - 20 μg L -1 for Tl, 0,1-5,0 μg L -1 for Co, 2-200 μg L -1 and for Cu e Ni 5-200 μg L -1 were obtained. The enrichment factors obtained ranged between 6 and 19. Recovery testing with the certified sample show ed recovery values (n = 3, certified values) after extraction of 105 and 101, 100 and 104% for Pb, Cd, Cu and Ni respectively. Samples of sweet waters of lake Jiqui, saline water from Potengi river and water produced from the oil industry (PETROBRAS) were spiked and the recovery (n = 3) for the analytes were between 80 and 112% confirming th at the proposed method can be used in the extraction. The proposed method enabled the sepa ration of metals from complex matrices, and with good pre-concentration factor, consistent with the MPV (allowed limits) compared to CONAMA Resolution No. 357/2005 which regulat es the quality of fresh surface water, brackish and saline water in Brazil.